Sodium Thiosulfate → HCID 11337042, compound

HRID 1985953Notes

Reaction equation

HRID 1985953 reaction equation
[Cl:1][C:2]1[S:6][C:5]([S:7]([NH:10][C@H:11]([CH2:19][OH:20])[C@H:12]([CH3:18])[CH2:13][C:14]([F:17])([F:16])[F:15])(=[O:9])=[O:8])=[CH:4][CH:3]=1.CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O.S([O-])([O-])(=O)=S.[Na+].[Na+]>C(Cl)Cl.CCOCC.C(=O)(O)[O-].[Na+].O.CCOC(C)=O.CCCCCC>[Cl:1][C:2]1[S:6][C:5]([S:7]([NH:10][C@H:11]([CH:19]=[O:20])[C@H:12]([CH3:18])[CH2:13][C:14]([F:15])([F:16])[F:17])(=[O:9])=[O:8])=[CH:4][CH:3]=1

Participants

9

Reactant 3

HCID 24477Sodium Thiosulfate2×HCID 159087TriacetoxyperiodinaneHCID 11291100HCID 11291100, compound

Product 1

HCID 11337042HCID 11337042, compoundYield 88.93%

Reagents, catalysts & solvents 5

HCID 962WaterSolvent2×HCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolvent2×HCID 516892Sodium BicarbonateSolventHCID 21226206Ethyl acetate hexaneSolvent

Conditions

Temperature
25 °C

Procedure

A solution of 5-chloro-N-[(1S,2R)-4,4,4-trifluoro-1-hydroxymethyl)-2-methylbutyl]thiophene-2-sulfonamide (prepared as in Example 1, 3.0 g, 8.53 mmol) in CH2Cl2 saturated with water (30 mL) was stirred under nitrogen at 0° C. Dess-Martin periodinane reagent (7.59 g, 17.90 mmol) was added in one portion. The resulting suspension was stirred at 25° C., monitoring the progress of reaction by TLC analysis (1:2 EtOAc/hexane). As the rate of conversion of the starting material slowed, additional 2 mL portions of CH2Cl2 saturated with water were added (three portions over 15 min). After 19 h at 25° C., the reaction was complete by TLC. The solution was diluted with Et2O (50 mL) and a solution of sodium thiosulfate, Na2S2O3 (93.83 mmol, 14.8 g, 11 eq) in 80% saturated aqueous sodium bicarbonate solution (50 mL) was added. The mixture was stirred rapidly for 10 min until both phases were clear. The layers were separated and the aqueous phase was extracted with ether (30 mL). The combined organic layers were washed sequentially with saturated aqueous sodium bicarbonate (10 mL) and brine (15 mL), then dried over MgSO4, filtered and concentrated to obtain a crude oil (2.67 g). The crude product was purified by the Biotage Flash™ 60 chromatography system, eluent: 1:6 EtOAc-hexanes, to afford 5-chloro-N-[(1S,2R)-4,4,4-trifluoro-1-formyl-2-methylbutyl]thiophene-2-sulfonamide as a colorless oil (2.65 g, 88.93%). Mass Spectrum (+ESI): 350 (M+H)+.

Workup

  1. stirringThe mixture was stirred rapidly for 10 min until both phases
  2. customThe layers were separated
  3. extractionthe aqueous phase was extracted with ether (30 mL)
  4. washThe combined organic layers were washed sequentially with saturated aqueous sodium bicarbonate (10 mL) and brine (15 mL)
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customto obtain a crude oil (2.67 g)
  9. customThe crude product was purified by the Biotage Flash™ 60 chromatography system, eluent

Sources & evidence

ORD record
ord-2fd10851afaa4095aa3d71cfb31c1920
Source dataset
uspto-grants-2009_06
Patent number
US07547725B2

Reaction notes

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